Colored curable resin composition, color filter, and display device

Abstract

The present invention addresses the problem of providing a colored curable resin composition with which a cured product can be formed that has sufficiently high haze and is not susceptible to causing sedimentation of particle components.　The present invention provides a colored curable resin composition containing a colorant, a resin, a polymerizable compound, a polymerization initiator, and acrylic particles. The colorant is a chromatic dye. The content of the acrylic particles is 1 mass% or more based on the total solid content of the colored curable resin composition.

Description

Color-curable resin composition, color filter, and display device

[0001] The present invention relates to a color-curable resin composition, a color filter, and a display device.

[0002] Color filters used in display devices such as liquid crystal displays, electroluminescent displays, and plasma displays; and in solid-state image sensors such as CCDs and CMOS sensors, are manufactured from color-curable resin compositions. Known compositions of this type include those containing colorants, resins, polymerizable compounds, polymerization initiators, inorganic fine particles, etc. (for example, Patent Document 1).

[0003] Japanese Patent Publication No. 2023-081304

[0004] Color filters used in display devices, solid-state image sensors, etc., are required to suppress ambient light reflection from the viewpoint of improving visibility. To suppress ambient light reflection, the haze of the color filter (cured product of a colored curable resin composition) must be sufficiently high. If the haze of the color filter is too low, the light scattering effect is small, and ambient light reflection tends to increase.

[0005] Furthermore, inorganic fine particles (e.g., silica particles) contained in conventional colored curable resin compositions tend to settle easily. When silica particles settle in a colored curable resin composition, the effect of suppressing external light reflection may decrease.

[0006] Therefore, the main objective of the present invention is to provide a colorable curable resin composition that can form a cured product having a sufficiently high haze and is less prone to the settling of particulate components.

[0007] The present invention provides the color-curable resin compositions described in [1] to [4], the color filter described in [5], and the display device described in [6]. [1] A color-curable resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator, and acrylic particles, wherein the colorant is a chromatic pigment, and the content of the acrylic particles is 1% by mass or more based on the total amount of solids in the color-curable resin composition. [2] The color-curable resin composition described in [1], wherein the content of the acrylic particles is 2% by mass or more based on the total amount of solids in the color-curable resin composition. [3] The color-curable resin composition described in [1] or [2], wherein the average particle diameter of the acrylic particles is 80 nm or more. [4] The color-curable resin composition described in any of [1] to [3], wherein the acrylic particles are solid acrylic particles. [5] A color filter formed from the color-curable resin composition described in any of [1] to [4]. [6] A display device comprising the color filter described in [5].

[0008] The present invention provides a color-curable resin composition that can form a cured product having a sufficiently high haze and is less prone to sedimentation of particulate components. The present invention also provides a color filter formed from such a color-curable resin composition, and a display device including the color filter.

[0009] The embodiments of the present invention will be described in detail below. However, the present invention is not limited to the embodiments described below.

[0010] In this specification, numerical ranges indicated using "~" represent a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described in stages within this specification, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described within this specification, the upper or lower limit of that numerical range may be replaced with the values ​​shown in the examples.

[0011] In this specification, (meth)acrylate means acrylate or the corresponding methacrylate. The same applies to other similar expressions such as (meth)acrylic acid, (meth)acryloyl, and (meth)acrylic acid esters.

[0012] In this specification, unless otherwise specified, the materials exemplified below may be used individually or in combination of two or more, to the extent that the conditions are met. The content of each component refers to the total amount of multiple substances corresponding to each component, unless otherwise specified.

[0013] [Colored Curable Resin Composition] The colored curable resin composition of this embodiment contains a colorant (hereinafter sometimes referred to as "component (A)"), a resin (hereinafter sometimes referred to as "component (B)"), a polymerizable compound (hereinafter sometimes referred to as "component (C)"), a polymerization initiator (hereinafter sometimes referred to as "component (D)"), and acrylic particles (hereinafter sometimes referred to as "component (E)"). The colored curable resin composition of this embodiment may also contain a solvent (hereinafter sometimes referred to as "component (F)"), a leveling agent (hereinafter sometimes referred to as "component (G)"), a coupling agent (hereinafter sometimes referred to as "component (H)"), and other components.

[0014] <Component (A): Colorant> Component (A) is a chromatic pigment. Here, a chromatic pigment is a pigment that exhibits color by absorbing light of a specific wavelength (more specifically, visible light between 300 and 800 nm) and reflecting or transmitting light of other wavelengths. Chromatic pigments are characterized by three elements: hue (type of color), saturation (vividness of color), and lightness (brightness of color). Component (A) can be said to be a pigment that is not an achromatic pigment. An achromatic pigment is a pigment that does not have hue or saturation and is characterized only by lightness. Achromatic pigments are, for example, pigments that exhibit colors such as white and black.

[0015] Examples of component (A) include pigments and dyes. Component (A) preferably includes a pigment. The pigment is not particularly limited, and known pigments can be used. Examples of pigments include those classified as pigments in the Color Index (published by The Society of Dyers and Colourists).

[0016] More specifically, C.I. Pigment Yellows 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, 185, 194, 214, 231, 235, 236, etc.; C.I. Pigment Oranges 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, etc.; C.I. Pigment reds such as 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 178, 179, 180, 190, 192, 202, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273, 291, 297, etc.; C.I. Pigment blues such as 15, 15:3, 15:4, 15:6, 16, 60, etc.; C.I. Pigment violets such as 1, 19, 23, 29, 32, 36, 38, etc.; C.I. Examples include green pigments such as Pigment Green 7, 36, 58, 59, 62, 63, 64, 65, 66, and 67; and brown pigments such as C.I. Pigment Brown 23 and 25.

[0017] The pigment may be subjected to rosin treatment, surface treatment using pigment derivatives into which acidic or basic groups have been introduced, grafting treatment of the pigment surface with polymer compounds, atomization treatment by sulfuric acid atomization method, washing treatment with solvents, water, etc. to remove impurities, or removal treatment of ionic impurities by ion exchange method, etc. The particle size of the pigment is preferably substantially uniform. The pigment can be dispersed by dispersing it with a pigment dispersant to obtain a pigment dispersion in which it is uniformly dispersed in a pigment dispersant solution. The pigments may be dispersed individually or multiple types may be mixed and dispersed.

[0018] Examples of pigment dispersants include surfactants such as silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric, polyester-based, polyamine-based, and acrylic-based surfactants. Examples of surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. Examples of commercially available surfactants include those with trade names such as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solpers (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF Japan Ltd.), Azisper (registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.), and Disperbyk (manufactured by Bic Chemie).

[0019] When a pigment dispersant is used, the amount used is preferably 10 to 200 parts by mass, more preferably 15 to 180 parts by mass, and even more preferably 20 to 160 parts by mass, per 100 parts by mass of pigment. When the amount of pigment dispersant used is within the above range, a pigment dispersion with a more uniform dispersion state tends to be obtained when two or more types of pigments are used.

[0020] The pigment content is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, even more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass, based on the total amount of component (A), and may also be 100% by mass.

[0021] The dye is not particularly limited, and known dyes can be used. Examples of dyes include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes include compounds classified as having hue other than pigments in the Color Index (published by The Society of Dyers and Colourists), and known dyes listed in the Dyeing Notes (Irozome-sha). In addition, based on chemical structure, examples include azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, phthalocyanine dyes, perylene dyes, quinophthalone dyes, and isoindoline dyes. Of these, the dye is preferably a solvent (organic solvent) soluble dye.

[0022] More specifically, C.I. Solvent Yellow 4, 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 117, 162, 163, 167, 189; C.I. Solvent Red 24, 45, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; C.I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 77, 86, 99; C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; C.I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 38, 44, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; C.I. C.I. Solvent Dyes such as Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35; C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 1 57, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 18 2, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 2 80, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, ​​383, 388, 394, 401, 412, 417, 418, 422, 426; C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173; C.I. Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102; C.I. Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 249, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, 340;C.I. Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109; etc. C.I. Acid Dyes, C.I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141; C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; C.I. Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 87, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166 ,167,168,170,171,172,173,188,189,190,192,193,194,195,196,198,199,200,201,202,203,207,209,210,212,213,214,222,225,226,228,229,236,237,238,242,243,244,245,246,247,248,249,250,251,252,256,257,259,260,268,274,275,293;C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, 82; and other C.I. Direct dyes; C.I. Disperse Yellow 51, 54, 76; C.I. Disperse Violet 26, 27; C.I. Disperse Blue 1, 14, 56, 60; and other C.I. Disperse dyes; C.I. Basic Red 1, 10; C.I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89; C.I. Basic Violet 2; C.I. Basic Red 9; C.I. Basic Green 1; and other C.I. Basic Dyes, C.I. Reactive Yellow 2, 76, 116; C.I. Reactive Orange 16; C.I. Reactive Red 36; and other C.I. Reactive Dyes, C.I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; C. I. Mordant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95; C. I. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; C. I. Mordant Violet 1, 1: 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58; C.I. Mordant Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;Examples include C.I. Mordant dyes such as C.I. Mordant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53; and C.I. Vat dyes such as C.I. Vat Green 1.

[0023] The dye content is preferably 0 to 50% by mass, more preferably 0 to 30% by mass, even more preferably 0 to 10% by mass, and particularly preferably 0 to 5% by mass, based on the total amount of component (A), and may also be 0% by mass.

[0024] The content of component (A) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and even more preferably 15 to 35% by mass, based on the total amount of solids in the colored curable resin composition. When the content of component (A) is within the above range, it tends to be easier to obtain the desired spectral characteristics and color density. In this specification, "total amount of solids in the colored curable resin composition" means the total amount of components excluding the solvent from the colored curable resin composition. The total amount of solids in the colored curable resin composition and the content of each component therein can be measured by known analytical means such as liquid chromatography and gas chromatography.

[0025] <Component (B): Resin> Component (B) is preferably an alkali-soluble resin. Examples of alkali-soluble resins include the following resins [K1] to [K6].

[0026] - Resin [K1]: A copolymer having structural units derived from at least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter sometimes referred to as "(a)") and structural units derived from a monomer (b) having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)"); - Resin [K3]: A copolymer having structural units derived from (a) and structural units derived from (c); - Resin [K4]: A copolymer having structural units obtained by adding (b) to a structural unit derived from (a) and structural units derived from (c); • Resin [K5]: A copolymer having structural units obtained by adding (a) to structural units derived from (b) and structural units derived from (c). • Resin [K6]: A copolymer having structural units obtained by adding (a) to structural units derived from (b) and further adding polycarboxylic acids and / or carboxylic acid anhydrides, and structural units derived from (c).

[0027] (a) includes, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid; and unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexenedicarboxylic acid; Bicyclounsaturated compounds containing carboxyl groups, such as methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; Examples include unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; unsaturated mono[(meth)acryloyloxyalkyl] esters of divalent or higher polycarboxylic acids such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate; and unsaturated acrylates containing both a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid.

[0028] Of these, (a) is preferably acrylic acid or methacrylic acid, considering its copolymerization reactivity and the solubility of the resulting (B) component in an alkaline aqueous solution.

[0029] (b) may be a polymerizable compound having, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0030] Examples of (b) include monomers having an oxyranyl group and an ethylenically unsaturated bond (b1) (hereinafter sometimes referred to as "(b1)"), monomers having an oxetanyl group and an ethylenically unsaturated bond (b2) (hereinafter sometimes referred to as "(b2)"), monomers having a tetrahydrofuryl group and an ethylenically unsaturated bond (b3) (hereinafter sometimes referred to as "(b3)"), and so on.

[0031] Examples of (b1) include monomers having a linear or branched aliphatic unsaturated hydrocarbon structure that has been epoxidized (b1-1) (hereinafter sometimes referred to as "(b1-1)") and monomers having a cyclic unsaturated hydrocarbon structure that has been epoxidized (b1-2) (hereinafter sometimes referred to as "(b1-2)").

[0032] Examples of (b1-1) include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, and the like.

[0033] Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celoxide 2000 (manufactured by Daicel Corporation)), 3,4-epoxycyclohexylmethyl acrylate (e.g., Cyclomer A400 (manufactured by Daicel Corporation)), 3,4-epoxycyclohexylmethyl methacrylate (e.g., Cyclomer M100 (manufactured by Daicel Corporation)), 3,4-epoxytricyclo[5.2.1.0 ２，６ decyl (meth)acrylate, the compound represented by formula (BI), the compound represented by formula (BII), and the like.

[0034]

[0035] In formula (BI) and formula (BII), ｅ R ｆ and ｅ R ｆ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group. ｇ X ｇ andｇ -S-, or *-R ｇ represents -NH-. R ｇ represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bond to O.

[0036] Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and the like.

[0037] Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, a 4-hydroxybutyl group, and the like.

[0038] R ｅ and R ｆ are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group.

[0039] Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, and the like.

[0040] X ｅ and X ｆ are preferably a single bond, a methylene group, an ethylene group, *-CH ２ -O-, or *-CH ２ CH ２ -O-, more preferably a single bond or *-CH ２ CH ２ -O- (* represents a bond to O.).

[0041] (b2) is preferably a monomer having an oxetanyl group and a (meth)acryloyloxy group. Examples of (b2) include 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, and 3-ethyl-3-acryloyloxyethyl oxetane.

[0042] (b3) is preferably a monomer having a tetrahydrofurfuryl group and a (meth)acryloyloxy group. Examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V#150 (manufactured by Osaka Organic Chemical Industry Co., Ltd.)) and tetrahydrofurfuryl methacrylate.

[0043] (b) is preferred in that, in the case of resin [K1] or resin [K2], the reliability of the resulting color filter, such as heat resistance and chemical resistance, can be made higher.

[0044] (c) For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ２，６ ] Decane-8-yl (meth)acrylate (in the relevant technical field, it is commonly called "dicyclopentanyl (meth)acrylate". It is also sometimes called "tricyclodecyl (meth)acrylate"), tricyclo[5.2.1.0 ２，６(Meth)acrylic acid esters such as decen-8-yl (meth)acrylate (commonly known as "dicyclopentenyl (meth)acrylate" in the relevant technical field), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate; hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybic Chlo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept -2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2- Bicyclounsaturated compounds such as ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N-(9-acridinyl)maleimide;Examples include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.

[0045] Of these, (c) is preferably (meth)acrylic acid esters.

[0046] In resin [K1], the ratio of structural units derived from each is preferably such that, of the total structural units constituting resin [K1], (a) is 2 to 60 mol% and (b) is 40 to 98 mol%, and more preferably (a) is 10 to 50 mol% and (b) is 50 to 90 mol%.

[0047] When the ratio of structural units of resin [K1] is within the above range, the colored curable resin composition tends to have excellent storage stability, developability when forming colored patterns, and solvent resistance of the resulting cured film.

[0048] The resin [K1] can be manufactured, for example, by referring to the method described in the literature "Experimental Methods for Polymer Synthesis" (authored by Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, March 1, 1972) and the cited literature.

[0049] Specifically, a method involves placing predetermined amounts of (a) and (b), a polymerization initiator, a solvent, etc., into a reaction vessel, creating a deoxygenated atmosphere by, for example, replacing oxygen with nitrogen, and heating and maintaining the temperature while stirring. The polymerization initiator and solvent used here are not particularly limited, and those commonly used in the field can be used. Examples of polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl2,2'-azobis(2-methylpropionate), etc.) and organic peroxides (benzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, etc.). As for the solvent, any solvent that dissolves each monomer can be used, for example, those exemplified by component (F) described later can be used.

[0050] The resulting copolymer may be used as is after the reaction, or a concentrated or diluted solution may be used. Alternatively, the resulting copolymer may be used after being extracted as a solid (powder) by methods such as reprecipitation. In particular, by using component (F) described later as a solvent during this polymerization, the solution after the reaction can be used in the preparation of the colored curable resin composition, thereby simplifying the manufacturing process of the colored curable resin composition of this embodiment.

[0051] In resin [K2], the ratio of structural units derived from each is preferably such that, out of the total structural units constituting resin [K2], (a) structural units: 2 to 45 mol%, (b) structural units: 2 to 95 mol%, and (c) structural units: 1 to 65 mol%, and more preferably such that (a) structural units: 5 to 40 mol%, (b) structural units: 5 to 80 mol%, and (c) structural units: 5 to 60 mol%.

[0052] When the ratio of structural units of resin [K2] is within the above range, the colored curable resin composition tends to exhibit excellent storage stability, developability when forming colored patterns, and solvent resistance, heat resistance, and mechanical strength of the resulting cured film.

[0053] Resin [K2] can be manufactured, for example, in the same manner as described as the method for manufacturing resin [K1].

[0054] In resin [K3], the ratio of structural units derived from each is preferably such that, of the total structural units constituting resin [K3], (a) is 2 to 60 mol% and (c) is 40 to 98 mol%, and more preferably (a) is 10 to 50 mol% and (c) is 50 to 90 mol%.

[0055] Resin [K3] can be manufactured, for example, in the same manner as described as the method for manufacturing resin [K1].

[0056] The resin [K4] can be produced by obtaining a copolymer of (a) and (c), and then adding the cyclic ether having 2 to 4 carbon atoms in (b) to the carboxylic acid and / or carboxylic acid anhydride in (a).

[0057] First, a copolymer of (a) and (c) is produced in the same manner as described for the production of resin [K1]. In this case, the ratio of structural units derived from each is preferably the same as that given for resin [K3].

[0058] Next, a cyclic ether having 2 to 4 carbon atoms in (b) is reacted with a portion of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer of (a) and (c).

[0059] Following the production of the copolymer of (a) and (c), the atmosphere inside the flask is replaced from nitrogen to air, and (b), a reaction catalyst for the reaction between a carboxylic acid or carboxylic acid anhydride and a cyclic ether (e.g., tris(dimethylaminomethyl)phenol, triphenylphosphine, etc.) and a polymerization inhibitor (e.g., hydroquinone, methoquinone, etc.) are added to the flask and the mixture is reacted at, for example, 60 to 130°C for 1 to 10 hours to produce resin [K4].

[0060] The amount of (b) used is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). This range tends to result in a good balance of storage stability of the colored curable resin composition, developability when forming a colored pattern, pattern shape, curability at low temperatures, and solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting colored pattern. Since the cyclic ether is highly reactive and unreacted (b) is less likely to remain, the (b) used in the resin [K4] is preferably (b1), more preferably (b1-1).

[0061] The amount of reaction catalyst used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b), and (c). The amount of polymerization inhibitor used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b), and (c).

[0062] The reaction conditions, such as the preparation method, reaction temperature, and time, can be adjusted as appropriate, taking into account the manufacturing equipment, the amount of heat generated by polymerization, etc. Similarly, the preparation method and reaction temperature can be adjusted as appropriate, taking into account the manufacturing equipment, the amount of heat generated by polymerization, etc.

[0063] As a first step, resin [K5] is produced in the same manner as resin [K1] to obtain a copolymer of (b) and (c). As described above, the obtained copolymer may be used as is after the reaction, or a concentrated or diluted solution may be used. The obtained copolymer may also be used after being extracted as a solid (powder) by methods such as reprecipitation.

[0064] The ratio of structural units derived from (b) and (c) is preferably such that, with respect to the total number of moles of all structural units constituting the copolymer, the ratio of structural units derived from (b) is 5 to 95 mol%, and the ratio of structural units derived from (c) is 5 to 95 mol%, and more preferably the ratio of structural units derived from (b) is 10 to 90 mol%, and the ratio of structural units derived from (c) is 10 to 90 mol%.

[0065] When the ratio of structural units of resin [K5] is within the above range, the storage stability of the colored curable resin composition, developability when forming colored patterns, pattern shape, curability at low temperatures, and the balance of solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting colored patterns tend to be good.

[0066] Furthermore, under the same conditions as for the production of resin [K4], resin [K5] can be obtained by reacting the cyclic ether derived from (b) in the copolymer of (b) and (c) with the carboxylic acid or carboxylic acid anhydride contained in (a).

[0067] The amount of (a) used to react with the copolymer is preferably 5 to 100 moles per 100 moles of (b). Because the cyclic ether is highly reactive and unreacted (b) is unlikely to remain, the (b) used in the resin [K5] is preferably (b1), more preferably (b1-1).

[0068] Resin [K6] is a resin obtained by further reacting resin [K5] with a polycarboxylic acid and / or carboxylic acid anhydride. The hydroxyl group generated by the reaction of a cyclic ether derived from (b) with a carboxylic acid or carboxylic acid anhydride derived from (a) is further reacted with a polycarboxylic acid and / or carboxylic acid anhydride.

[0069] Examples of polycarboxylic acids include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, and tricarbanilic acid. Examples of carboxylic acid anhydrides include succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride. The amount of polycarboxylic acid and / or carboxylic acid anhydride used is preferably 0.05 to 1 mole, more preferably 0.1 to 0.5 moles, per 1 mole of the amount of (a) used.

[0070] Component (B) is preferably a resin having structural units with ethylenically unsaturated bonds in the side chains (resin [K4] or resin [K5]), more preferably a resin having structural units containing (meth)acryloyl groups in the side chains.

[0071] Resins having structural units containing a (meth)acryloyl group in the side chain are preferably resins [K4] that use monomers having a (meth)acryloyl group as (b), such as glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-methyl-3-methacryloyloxymethyl oxetane, and tetrahydrofurfuryl acrylate, and resins [K5] that use monomers having a (meth)acryloyl group as (a), such as acrylic acid, methacrylic acid, and mono[2-(meth)acryloyloxyethyl] succinate.

[0072] The weight-average molecular weight of component (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 4,000 to 50,000, and even more preferably 5,000 to 30,000. When the weight-average molecular weight of component (B) in terms of polystyrene is within the above range, the hardness of the cured film of the colored curable resin composition is improved, the residual film rate is high, the solubility of the unexposed areas in the developer is good, the pattern shape is improved, and the resolution of the colored pattern tends to improve.

[0073] The degree of dispersion of component (B) [weight-average molecular weight (Mw) / number-average molecular weight (Mn)] is preferably 1.1 to 6, and more preferably 1.2 to 4.

[0074] The acid value of component (B) is preferably 10 to 170 mg-KOH / g, more preferably 20 to 150 mg-KOH / g, and even more preferably 30 to 135 mg-KOH / g, on a solid content basis. Here, the acid value is measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of component (B), and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

[0075] The content of component (B) is preferably 1 to 60% by mass, more preferably 3 to 50% by mass, and even more preferably 5 to 45% by mass, based on the total amount of solids in the colored curable resin composition. When the content of component (B) is within the above range, it is easier to prevent aggregation of component (E) and suppress sedimentation, thus improving sedimentation properties. Furthermore, by adsorbing onto the particle surface of component (E), it is easier to suppress the generation of residuals derived from component (E) after the development process, resulting in good developability.

[0076] <Component (C): Polymerizable Compound> Component (C) is a compound that can be polymerized by active radicals and / or acids generated from component (D) described below. Examples of component (C) include compounds having an ethylenically unsaturated bond. Component (C) is preferably a compound having a (meth)acryloyl group. By having a compound having a (meth)acryloyl group as component (C), it is possible to obtain a cured product with excellent pattern-forming properties in a colored curable resin composition.

[0077] Component (C) is preferably a compound having two or more (meth)acryloyl groups, and more preferably a compound having three or more (meth)acryloyl groups.

[0078] Examples of compounds having two (meth)acryloyl groups include 1,3-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bis(acryloyloxyethyl) ether of bisphenol A, ethylene oxide-modified bisphenol A di(meth)acrylate, propylene oxide-modified neopentyl glycol di(meth)acrylate, ethylene oxide-modified neopentyl glycol di(meth)acrylate, and 3-methylpentanediol di(meth)acrylate.

[0079] Compounds having three or more (meth)acryloyl groups include, for example, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol poly(meth)acrylate (e.g., pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate), dipentaerythritol poly(meth)acrylate (e.g., dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate), tripentaerythritol poly(meth)acrylate Tri(meth)acrylate (e.g., tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate), tetrapentaerythritol poly(meth)acrylate (e.g., tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate), tris(2-(meth)acryloyloxyethyl) isocyanurate, ethylene oxide-modified glycerin tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth) Acrylates, ethylene oxide-modified pentaerythritol poly(meth)acrylates (e.g., ethylene oxide-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate), ethylene oxide-modified dipentaerythritol poly(meth)acrylates (e.g., ethylene oxide-modified dipentaerythritol penta(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate), propylene oxide-modified glycerides Ricelin tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified pentaerythritol poly(meth)acrylate (e.g., propylene oxide-modified pentaerythritol tri(meth)acrylate, propylene oxide-modified pentaerythritol tetra(meth)acrylate), propylene oxide-modified dipentaerythritol poly(meth)acrylate (e.g., propylene oxide-modified dipentaerythritol penta(meth)acrylate,Examples include propylene oxide-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol poly(meth)acrylate (e.g., caprolactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate), and caprolactone-modified dipentaerythritol poly(meth)acrylate (e.g., caprolactone-modified dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate).

[0080] The molecular weight or weight-average molecular weight of component (C) is preferably 150 to 2900, more preferably 200 to 1500.

[0081] The content of component (C) is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, and even more preferably 5 to 30% by mass, based on the total amount of solids in the colored curable resin composition. When the content of component (C) is within the above range, the degree of curing of the cured coating film by exposure can be increased, and component (E) is less likely to detach during the development process, so haze tends to be improved.

[0082] <Component (D): Polymerization initiator> Component (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc., upon the action of light or heat and initiate polymerization; known polymerization initiators can be used. Examples of polymerization initiators that generate active radicals include O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, and biimidazole compounds.

[0083] O-acyloxime compounds are compounds having a substructure represented by formula (D1). Hereafter, * represents a bond.

[0084]

[0085] Examples of O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, and N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl Examples include {-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazole-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-one-2-imine, and N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine. As the O-acyloxime compound, commercially available products such as Irgacure® (registered trademark, hereinafter the same) OXE01 (N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine), Irgacure OXE02 (N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine) (both manufactured by BASF), and N-1919 (manufactured by ADEKA Corporation) may be used.

[0086] Among these, the O-acyloxime compounds are preferably N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, and N-benzoyl At least one compound selected from the group consisting of ruoxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, more preferably N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, or N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine. Using such an O-acyloxime compound tends to yield a color filter with high brightness.

[0087] Alkylphenone compounds are compounds having a substructure represented by formula (D2) or formula (D3). In these substructures, the benzene ring may have substituents.

[0088]

[0089] Examples of compounds having the substructure represented by formula (D2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one. Commercially available products such as Irgacure 369, 907, and 379 (all manufactured by BASF) may also be used as compounds having the substructure represented by formula (D2).

[0090] Examples of compounds having the substructure represented by formula (D3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyldimethyl ketal.

[0091] Alkylphenone compounds are preferably those having a substructure represented by formula (D2) in terms of sensitivity.

[0092] Examples of triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2 Examples include -(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

[0093] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercially available acylphosphine oxide compounds such as Irgacure 819 (manufactured by BASF) may also be used.

[0094] Examples of biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Publication No. 6-75372, Japanese Patent Publication No. 6-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl Examples include biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, Japanese Patent Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, etc.), and biimidazole compounds in which the phenyl group at the 4,4',5,5'-position is substituted with a carboalkoxy group (see, for example, Japanese Patent Application Publication No. 7-10913, etc.).

[0095] Furthermore, component (D) includes benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; and 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with component (Da) (especially amines) described later.

[0096] Examples of polymerization initiators that generate acids include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, and diphenyliodonium hexafluoroantimonate, as well as nitrobenzyl tosylates and benzoin tosylates.

[0097] Component (D) is preferably a polymerization initiator comprising at least one selected from the group consisting of O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, and biimidazole compounds, and more preferably a polymerization initiator comprising an O-acyloxime compound.

[0098] The content of component (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of components (B) and (C). When the content of component (D) is within the above range, the degree of hardening of the cured coating film due to exposure can be increased, and component (E) is less likely to detach during the development process, so the haze tends to be good.

[0099] <Component (Da): Polymerization Initiator> Component (Da) is a compound or sensitizer used to promote the polymerization of polymerizable compounds. When a colored curable resin composition contains component (D), it is usually used in combination with component (D).

[0100] Examples of component (Da) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

[0101] Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michla's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone. Commercially available amine compounds such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may also be used. Among these, 4,4'-bis(diethylamino)benzophenone is preferred as the amine compound.

[0102] Examples of alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and 2-ethyl-9,10-dibutoxyanthracene.

[0103] Examples of thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0104] Examples of carboxylic acid compounds include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

[0105] When using these (Da) components, their content is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of (B) and (C) components. When the amount of (Da) component is within this range, the degree of hardening of the cured coating film due to exposure can be increased, and the (E) component is less likely to detach during the development process, so haze tends to be improved. Furthermore, by adsorbing onto the particle surface of the (E) component, it becomes easier to suppress the generation of residuals originating from the (E) component after the development process, resulting in improved developability.

[0106] <Component (E): Acrylic Particles> Component (E) consists of hollow or solid particles made from acrylic resin. Here, acrylic resin refers to a polymer (resin) obtained by polymerizing either acrylic acid ester or methacrylic acid ester, or both, as part of the raw materials. Hollow particles refer to particles that have a cavity inside. Hollow particles made from acrylic resin are hollow acrylic particles. Solid particles refer to particles that do not have a cavity inside and are composed of a uniform composition. Solid particles made from acrylic resin are solid acrylic particles.

[0107] The color-curable resin composition of this embodiment contains component (E), which improves the haze of the color filter (cured product of the color-curable resin composition). Acrylic resins have a lower specific gravity than silica. Since haze depends on the number of particles, component (E) can be added in a larger number of particles compared to silica particles of the same mass, and therefore tends to improve haze more easily. In addition, because acrylic resins have a lower specific gravity than silica, component (E) is less likely to settle compared to silica particles.

[0108] Component (E) may be, for example, particles mainly composed of PMMA (polymethyl methacrylate), or particles copolymerized with styrene or the like. From the viewpoint of maintaining shape, component (E) is preferably crosslinked acrylic particles. From the viewpoint of improving haze, component (E) is preferably solid acrylic particles.

[0109] Component (E) may be manufactured by known methods or a commercially available product may be used as is. Examples of commercially available components (E) include Techpolymer® SSX, BMSA, and XX series (manufactured by Sekisui Chemical Co., Ltd.).

[0110] The average particle size of component (E) is preferably 60 nm or more. When the average particle size of component (E) is 60 nm or more, the haze of the resulting cured product can be sufficiently improved. The average particle size of component (E) is more preferably 80 nm or more, even more preferably 100 nm or more, particularly preferably 300 nm or more, especially preferably 500 nm or more, and most preferably 750 nm or more. The average particle size of component (E) is preferably 5000 nm or less, more preferably 3000 nm or less, even more preferably 2000 nm or less, and particularly preferably 1600 nm or less.

[0111] In this specification, the average particle size refers to the number-based median diameter (Dn50) in the particle size distribution of primary particles determined by dynamic light scattering.

[0112] The content of component (E) is 1% by mass or more, based on the total amount of solids in the colored curable resin composition. When the content of component (E) is 1% by mass or more, based on the total amount of solids in the colored curable resin composition, the haze of the resulting cured product tends to be sufficiently high. The content of component (E) is preferably 2% by mass or more, based on the total amount of solids in the colored curable resin composition. The content of component (E) is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less, based on the total amount of solids in the colored curable resin composition.

[0113] <Component (F): Solvent> Component (F) is not particularly limited, and any solvent commonly used in the field may be used. Examples include ester solvents (solvents containing -COO- in the molecule but not -O-), ether solvents (solvents containing -O- in the molecule but not -COO-), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule but not -COO-), alcohol solvents (solvents containing OH in the molecule but not -O-, -CO-, and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxides, etc.

[0114] Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0115] Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethole, and methylanisole.

[0116] Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxypropionate Examples include ethyl xy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0117] Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone (methyl isobutyl ketone), cyclopentanone, cyclohexanone, and isophorone.

[0118] Examples of alcoholic solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0119] Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

[0120] Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0121] Among these, component (F) is preferably at least one selected from the group consisting of ether ester solvents and ether solvents, more preferably propylene glycol monomethyl ether acetate or diethylene glycol ethyl methyl ether.

[0122] The content of component (F) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the total amount of the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass, based on the total amount of the colored curable resin composition. When the content of component (F) is within the above range, it is possible to adjust the unevenness of the coating film caused by the accumulation of component (E) on the coating film surface, thereby obtaining good haze. In addition, it is possible to suppress the aggregation and sedimentation of component (E), and there is a tendency for good sedimentation properties.

[0123] <Component (G): Leveling agent> Examples of component (G) include silicone surfactants, fluorine surfactants, and silicone surfactants containing fluorine atoms. These may have polymerizable groups in their side chains.

[0124] Examples of silicone-based surfactants include surfactants having siloxane bonds in their molecules. Specifically, examples include Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (product names, manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan LLC).

[0125] Examples of fluorine-based surfactants include surfactants having fluorocarbon chains in their molecules. Specifically, these include Florard® FC430 and FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac® F142D, F171, F172, F173, F177, F183, F554, R30, and RS-718-K (manufactured by DIC Corporation), F-Top® EF301, EF303, EF351, and EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon® S381, S382, SC101, and SC105 (manufactured by AGC Inc. (formerly Asahi Glass Co., Ltd.)), and E5844 (manufactured by Daikin Fine Chemical Laboratories, Inc.).

[0126] Examples of silicone-based surfactants containing fluorine atoms include surfactants having siloxane bonds and fluorocarbon chains in their molecules. Specifically, examples include Megafac® R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

[0127] The content of component (G) is preferably 0.001 to 0.5% by mass, more preferably 0.002 to 0.3% by mass, and even more preferably 0.01 to 0.2% by mass, based on the total amount of solids in the colored curable resin composition. When the content of component (G) is within the above range, it is possible to adjust the unevenness of the coating film caused by the accumulation of component (E) on the coating film surface, and good haze can be achieved.

[0128] <(H) component: coupling agent> Examples of (H) component include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane Examples include sisilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, and 3-glycidoxypropylethoxydimethylsilane.

[0129] Examples of commercially available products containing component (H) include KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, and KBE-5 Examples of silane coupling agents manufactured by Shin-Etsu Chemical Co., Ltd. include 02, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, and KBE-9007.

[0130] The content of component (H) is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 2.0% by mass, and even more preferably 0.1 to 1.5% by mass, based on the total amount of solids in the colored curable resin composition.

[0131] <Other Components> The colored curable resin composition of this embodiment may optionally contain additives known in the art, such as dispersants, ultraviolet absorbers, fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents.

[0132] The colored curable resin composition of this embodiment can be prepared, for example, by mixing components (A), (B), (C), (D), and (E), as well as components (Da), (F), (G), (H), and other components as needed. It is preferable to filter the colored curable resin composition through a filter with a pore size of about 0.01 to 10 μm after mixing the components.

[0133] The color-curable resin composition of this embodiment is suitably used for forming color filters.

[0134] [Color filter and method for manufacturing the same] Methods for manufacturing a colored pattern from the color-curable resin composition of this embodiment include photolithography, inkjet printing, and printing. Among these, photolithography is preferred as the method for manufacturing the colored pattern. Photolithography is a method in which the color-curable resin composition is applied to a substrate, dried to form a colored coating film, and the colored coating film is exposed to light through a photomask for development. In photolithography, by not using a photomask during exposure and / or by not developing, a color-cured coating film, which is a cured product of the colored coating film, can be formed. The colored pattern (pattern color-cured coating film) or color-cured coating film formed in this way is the color filter of this embodiment.

[0135] The film thickness of the color filter to be manufactured is not particularly limited and can be adjusted as appropriate depending on the purpose and application. The film thickness of the color filter may be, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

[0136] Examples of substrates include glass plates such as quartz glass, borosilicate glass, aluminasilate glass, and soda-lime glass with a silica coating on the surface; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; silicon substrates; and substrates on which thin films of aluminum, silver, or silver / copper / palladium alloys are formed. Other color filters (colored patterns or colored hardened coatings), resin films, transistors, circuits, etc., may be formed on these substrates.

[0137] The formation of each color pixel by photolithography can be carried out using known or conventional equipment and conditions. For example, each color pixel can be fabricated by photolithography as described below.

[0138] First, a colored curable resin composition is applied to a substrate, and volatile components such as solvents are removed by heat drying (pre-baking) and / or vacuum drying, and then dried to obtain a smooth colored coating.

[0139] Coating methods include spin coating, slit coating, and slit and spin coating. When performing heat drying, the temperature is preferably 30 to 120°C, more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. When performing vacuum drying, it is preferable to do so under a pressure of 50 to 150 Pa and at a temperature range of 20 to 25°C.

[0140] The thickness of the colored coating is not particularly limited and can be appropriately selected according to the desired thickness of the color filter.

[0141] Next, the colored coating is exposed through a photomask to form the desired color pattern. The pattern formed by the photomask is not particularly limited, and a pattern suitable for the intended application can be used.

[0142] The light source used for exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. The light source used for exposure may, for example, cut out light below 350 nm using a filter that cuts out this wavelength range, or it may selectively extract light around 436 nm, around 408 nm, and around 365 nm using a bandpass filter that extracts these wavelength ranges. Specific examples of light sources used for exposure include mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, etc.

[0143] In exposure, it is preferable to use an exposure apparatus such as a mask aligner and a stepper, as this allows for uniform irradiation of the entire exposure surface with parallel light rays and enables precise alignment between the photomask and the substrate on which the colored coating has been formed.

[0144] A colored pattern is formed on the substrate by developing the colored coating film (i.e., the colored and cured coating film) after exposure by contacting it with a developer. During development, the unexposed parts of the colored and cured coating film are dissolved and removed by the developer. Examples of the developer include aqueous solutions (aqueous developers) containing alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide. The concentration of the alkaline compound in these aqueous developers is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. The developer may further contain a surfactant.

[0145] Development methods include the paddle method, dipping method, and spray method. During development, the substrate may be tilted at any angle. After development, it is preferable to wash the obtained colored pattern with water.

[0146] It is preferable to perform post-baking on the obtained coloring pattern. The post-baking temperature is preferably 60 to 250°C, more preferably 70 to 120°C. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

[0147] [Display device and solid-state image sensor] The display device of this embodiment includes a color filter which is a colored pattern, a colored cured coating, etc. The solid-state image sensor of this embodiment includes a color filter which is a colored pattern, a colored cured coating, etc.

[0148] According to the color-curable resin composition of this embodiment, for example, a color filter can be manufactured. This color filter is useful as a film used in display devices such as liquid crystal displays, electroluminescent displays, and plasma displays; and in solid-state image sensors such as CCDs and CMOS sensors.

[0149] The present invention will be described in more detail below with reference to examples, but the present invention is not limited by the following examples, and it is certainly possible to implement it with appropriate modifications within the scope that is consistent with the spirit of the above and below, and all such modifications are included within the technical scope of the present invention. In the following, unless otherwise specified, "parts" means "parts by mass" and "%" means "percent mass".

[0150] In the following examples, "room temperature" means 18 to 24°C.

[0151] In the following examples, the structure of the compounds was confirmed using a mass spectrometer (LC: Agilent Model 1200, MASS: Agilent Model LC / MSD6130).

[0152] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the resin, converted to polystyrene, were measured by the GPC method under the following conditions: Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation) Column: TSK-GELG2000HXL Column temperature: 40°C Solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Solid content concentration of analytical sample: 0.001–0.01% by mass Injection volume: 50 μL Detector: RI Calibration standards: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

[0153] (Synthesis Example 1) <Preparation of Resin Solution (B1)> 349 parts of propylene glycol monomethyl ether acetate were added to a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, and the mixture was stirred while purging with nitrogen and heated to 120°C. Next, 23.4 parts of tert-butyl peroxy-2-ethylhexanoate were added to a monomer mixture consisting of 169.2 parts benzyl methacrylate, 103.3 parts methacrylic acid, and 52.9 parts dicyclopentanyl methacrylate, and this mixture was added dropwise to the flask from the dropping funnel over a period of 2 hours. After the addition was complete, the mixture was stirred for a further 30 minutes to carry out the copolymerization reaction. After that, the flask was purged with air, and 51.2 parts glycidyl methacrylate, 1.1 parts triphenylphosphine, and 1.1 parts methoquinone were added, and the reaction was continued at 120°C for 10 hours to obtain a copolymer (resin). Finally, propylene glycol monomethyl ether acetate was added to the reaction solution to obtain a resin solution (B1) with a solid content concentration of 40%. The weight-average molecular weight Mw of the copolymer (resin) was 10300, and the solid content acid value was 120.9 mgKOH / g.

[0154] (Synthesis Example 2) <Preparation of Resin Solution (B2)> 386 parts of propylene glycol monomethyl ether were added to a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, and the mixture was stirred while purging with nitrogen and heated to 90°C. Next, 61.5 parts of dimethyl 2,2'-azobis(2-methylpropionate) were added to a monomer mixture consisting of 147 parts of malonic acid-2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester, 285 parts of 2-ethylhexyl acrylate, 50 parts of 2-hydroxyethyl methacrylate, 26 parts of methacrylic acid, 183 parts of propylene glycol monomethyl ether, and 234 parts of propylene glycol monomethyl ether acetate, and this mixture was added dropwise to the flask from the dropping funnel over a period of 1 hour. After the dropwise addition was complete, the mixture was stirred for a further 2 hours to carry out the copolymerization reaction and obtain a copolymer (resin). Finally, propylene glycol monomethyl ether acetate was added to the reaction solution to obtain resin (B2) solution, with a solid content concentration of 35%. The weight-average molecular weight Mw of the copolymer (resin) was 9000, and the solid content acid value was 32.7 mgKOH / g.

[0155] (Synthesis Example 3) <Preparation of Colorant Dispersion (A1)> The following components were mixed and the pigment was thoroughly dispersed using a bead mill to obtain a colorant dispersion (A1). C.I. Pigment Red 291: 12.9 parts C.I. Pigment Yellow 139: 1.0 part Acrylic pigment dispersant: 4.4 parts Propylene glycol monomethyl ether: 8.0 parts Propylene glycol monomethyl ether acetate: 73.7 parts

[0156] (Synthesis Example 4) <Preparation of Colorant Dispersion (A2)> The following components were mixed and the pigment was thoroughly dispersed using a bead mill to obtain a colorant dispersion (A2). C.I. Pigment Green 59: 9.6 parts C.I. Pigment Yellow 150: 1.7 parts C.I. Pigment Yellow 139: 1.5 parts Acrylic Pigment Dispersant: 3.1 parts Propylene Glycol Monomethyl Ether Acetate: 84.0 parts

[0157] (Synthesis Example 5) <Preparation of Colorant Dispersion (A3)> The following components were mixed and the pigment was thoroughly dispersed using a bead mill to obtain a colorant dispersion (A3). C.I. Pigment Green 36: 7.0 parts C.I. Pigment Yellow 139: 1.5 parts C.I. Pigment Yellow 150: 5.8 parts Acrylic Pigment Dispersant: 4.0 parts Propylene Glycol Monomethyl Ether Acetate: 81.7 parts

[0158] (Synthesis Example 6) <Preparation of Colorant Dispersion (A4)> The following components were mixed and the pigment was thoroughly dispersed using a bead mill to obtain a colorant dispersion (A4). C.I. Pigment Blue 15:6:10.5 parts C.I. Pigment Violet 23:3.8 parts Acrylic Pigment Dispersant: 4.0 parts Propylene Glycol Monomethyl Ether Acetate: 81.7 parts

[0159] (Synthesis Example 7) <Preparation of Silica Dispersion (e1)> A silica dispersion (e1) was obtained by mixing the following components and thoroughly dispersing silica particles (average particle size 422 nm) using a bead mill. Silica particles: 20 parts Copolymer of resin solution (B1) from Synthesis Example 1 (on a solid content basis): 2 parts Propylene glycol monomethyl ether acetate: 78 parts

[0160] (Examples 1-13 and Comparative Examples 1 and 2) <Preparation of Colored Curable Resin Compositions> The components listed in Tables 1 and 2 were mixed in the amounts listed in Tables 1 and 2 to obtain the colored curable resin compositions of Examples 1-7 and Comparative Examples 1 and 2. The unit of the amount of each component in Tables 1 and 2 is "parts". The amounts of (A1), (A2), (A3), (A4), (B1), (B2), (E1), (E2), (E3), (E4), (E5), and (e1) are the amounts of dispersion or solution.

[0161] The symbols in Tables 1 and 2 are as follows: (A) Component: Colorant (A1): Colorant dispersion of Synthesis Example 3 (A1) (A2): Colorant dispersion of Synthesis Example 4 (A2) (A3): Colorant dispersion of Synthesis Example 5 (A3) (A4): Colorant dispersion of Synthesis Example 6 (A4) (B) Component: Resin (B1): Resin solution of Synthesis Example 1 (B1) (B2): Resin solution of Synthesis Example 2 (B2) (C) Component: Polymerizable compound (C1): Glycerin triacrylate (Aronics® M-930 (manufactured by Toagosei Co., Ltd.)) (C2): Dipentaerythritol polyacrylate (A-9550 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)) (D) Component: Polymerization initiator (D1): N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine (PBG-327, O-acyloxime compound (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.)) (D2): Carbazole oxime ester (IW-15, Nippon Chemical Industries, Ltd.) (E) component: acrylic particles (E1): solid acrylic particle dispersion (Techpolymer® SSX-101 (manufactured by Sekisui Chemicals Co., Ltd.), average particle size 1592 nm, 10% propylene glycol monomethyl ether acetate dispersion) (E2): solid acrylic particle dispersion (average particle size 785 nm, 23.1% propylene glycol monomethyl ether acetate dispersion) (E3): Hollow acrylic particle dispersion (Techpolymer® XX-420K (manufactured by Sekisui Chemical Co., Ltd.), average particle size 62 nm, 17.1% propylene glycol monomethyl ether acetate dispersion) (E4): Hollow acrylic particle dispersion (Techpolymer® XX-421K (manufactured by Sekisui Chemical Co., Ltd.), average particle size 79 nm, 14.7% propylene glycol monomethyl ether acetate dispersion) (E5): Solid acrylic particle dispersion (Techpolymer® XX-423K (manufactured by Sekisui Chemical Co., Ltd.), average particle size 383 nm, 10% propylene glycol monomethyl ether acetate dispersion) (e) component: silica particles (e1): silica dispersion of synthesis example 7 (e1) (F) component: solvent (F1): propylene glycol monomethyl ether acetate (G) component: leveling agent(G1): Polyether-modified silicone oil (Toray Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.)

[0162] <Measurement of Average Particle Size of Acrylic Particles in Dispersion> The average particle size of acrylic particles was measured using the following procedure. The acrylic particles were diluted with propylene glycol monomethyl ether acetate to a particle concentration of 1 mg / mL, then filtered through a 5 μm filter (PTFE Syring Filter (Membrane Solutions), 13 mm diameter, Pore Size 5 μm), and then Dn50 (number-based median diameter) was measured using a dynamic light scattering particle size distribution analyzer (Zetasizer Ultra Red Label (Malvern Panalogical)) under the following conditions. The measurement was performed with N=2, and the average value was taken as the average particle size of the acrylic particles in the particle dispersion. (Measurement conditions) Laser wavelength: 632.8 nm Solvent viscosity: 1.1 mPa·s Solvent refractive index: 1.40 Sample refractive index: 1.48 (solid acrylic particles), 1.59 (hollow acrylic particles) Measurement temperature: 25°C Measurement mode: Particle size calculation conditions: General-purpose model

[0163]

[0164]

[0165] <Preparation of Colored Cured Films> The colored curable resin compositions of Examples 1 to 13 and Comparative Examples 1 and 2, prepared as described above, were applied by spin coating onto a 5 cm square glass substrate (Eagle 2000 (Corning)) to a post-baking film thickness of 2.5 μm. After pre-baking at 85°C for 2 minutes, a colored coating film was formed. After cooling, the colored coating film formed on the substrate was exposed to 100 mJ / cm² in an air atmosphere using an exposure machine (TME-150RSK (Topcon Corporation)). ２ The samples were irradiated with light at an exposure level of 365 nm. After light irradiation, post-baking was performed in an oven at 85°C for 30 minutes to obtain the colored cured films of Examples 1 to 13 and Comparative Examples 1 and 2.

[0166] <Measurement of Haze> The haze of the obtained colored cured film was measured using a Haze Meter HZ-2 (manufactured by Suga Test Instruments Co., Ltd.). The results are shown in Tables 3 and 4. A haze of 2% or more indicates good suppression of external light reflection.

[0167] <Evaluation of Sedimentation> 20 mL of the colored curable resin compositions of Examples 1-13 and Comparative Examples 1 and 2 were dispensed into 30 mL glass vials and left to stand at room temperature for 24 hours. After that, the presence or absence of precipitate at the bottom of the glass vials was visually checked, and the sedimentation of component (E) or component (e) was evaluated. If no precipitate was observed after 24 hours of standing, it was classified as "A" as sedimentation was unlikely to occur, and if precipitate was observed after 24 hours of standing, it was classified as "B". The results are shown in Tables 3 and 4.

[0168]

[0169]

[0170] As shown in Tables 3 and 4, sedimentation of particulate components was observed in the colored curable resin composition of Comparative Example 2. In contrast, no such sedimentation of particulate components was observed in the colored curable resin compositions of Examples 1 to 13, and the haze was sufficiently higher compared to the colored curable resin composition of Comparative Example 1. Furthermore, a comparison between Example 4 and Examples 6 and 7 revealed that when the acrylic particles are solid acrylic particles, the haze tends to be higher. These results confirm that the colored curable resin composition of the present invention can form a cured product with sufficiently high haze and is less prone to sedimentation of particulate components.

Claims

1. A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator, and acrylic particles, wherein the colorant is a chromatic pigment, and the content of the acrylic particles is 1% by mass or more based on the total amount of solids in the colored curable resin composition.

2. The colored curable resin composition according to claim 1, wherein the content of the acrylic particles is 2% by mass or more, based on the total amount of solids in the colored curable resin composition.

3. The colored curable resin composition according to claim 1, wherein the average particle size of the acrylic particles is 80 nm or more.

4. The colored curable resin composition according to claim 1, wherein the acrylic particles are solid acrylic particles.

5. A color filter formed from a color-curable resin composition according to any one of claims 1 to 4.

6. A display device comprising the color filter described in claim 5.

Images